New composition of matter and methods involving the use of said composition of matter



United States Patent 3,081,190 NEW COMPOSITION OF MATTER AND METHODS INVOLVING THE USE OF SAID COMPOSITION OF MATTER 7 Carl E. Johnson, Glen Ellyn, Ill., assignor to Nalco Chemical Company, Chicago, Ill., a corporation of Delaware No Drawing. Filed Dec. 14, 1959, Ser. No. 859,139 21 Claims. (Cl. 117--62) The present invention relates to new compositions of matter. More particularly, the invention is directed to mixtures of alkali metal salts of amphoteric metals and water-soluble soaps; to precipitates formed when the pH of said mixtures is lowered; and to the use of said mixtures and precipitates for various purposes.

In manufacturing paper, and especially newsprint, it is necessary to add a number of substances to the cellulosic fibers in the pulp stock. Virtually all paper except the absorbent type and filter paper contains finely ground filler. The purpose of the filler is to occupy the spaces between fibers which gives the paper a smooth surface, a more brilliant whiteness, improved printability, and improved opacity. Sizing agents are also added to most pulp stocks. The function of the sizing is to give paper a resistance to penetration of liquids. Common sizing agents include Wax emulsions or soaps which are made by sapon fying rosin with an alkali. The sizes are precipitated with alum in order to form a bond between the cellulose fibers and the rosin fatty acids through the aluminum ion.

The use of alum to precipitate sodium ro-sinate has created certain problems. It often happens, for example, that residual acids are present in the paper in the form of basic aluminum sulfates after the size has been set. This is objectionable because paper containing free acid has poor aging properties.

It is one object of the present invention to provide an improved sizing agent for use in manufacturing paper.

Anotherob ject of the invention is to provide a new composition of matter from which a sizecan be precipitated at an alkaline pH.

"There are a number of potential industrial uses both for aqueous solutions having relatively hi h viscosities and for compounds which cause liquids to thicken. Materials of this type, for example, could be added to shampoos to increase the thickness of the shampoo without increasing the quantity of dissolved solids. Water itself cannot be used as a fluid for hydraulic systems because its viscosity is too low and because it has no lubricating properties. Itwould be most helpful if a suitable thickening agent could be found which, when added to water, would provide a liquid having suitable viscosity and lubricating characteristics. A hydraulic fluid of this nature would be both noninflammable and inexpensive.

Another object of the present invention. therefore, is to provide a satisfactory water based hydraulic fluid.

Still another object is to provide a shampoo and a bar soap having high water concentrations but which lather" Other objects will become apparent to those skilled in can be prepared by any one of several methods.

such method is the caustic-alumina fusion technique.

. 2 the art from the following detailed description of the invention.

In general, the present invention involves the discovery of certain new compositions of matter which include (1) an aqueous solution containing an alkali metal salt of an amphoteric metal and a water-soluble soap, and (2) the precipitate which is formed when this mixture is contacted with an acidic solution. More particularly, the invention is directed to the said compositions of matter and to the use of these materials in various processes and in preparing various products.

in the following description aluminum is specifically mentioned as the amphoteric metal of the subject compositions. It should be remembered, however, that the alkali metal salts of zinc, titanium, and tin could be used in place of the alkali metal aluminates in each of the processes and in preparing my various products.

The novel solutions are prepared by mixing an alkali metal aluminate such as sodium aluminate or potassium aluminate with a water-soluble soap. In forming the mixture, an aqueous solution containing sodium or potassium aluminate is combined with an aqueous soap solu-.

tion. It has been found that the ratio of aluminate to soap can vary from about .5 part by Weight of aluminate to one part by weight of soap to as high as 10 parts by weight aluminate to one part by weight soap. Wherethe aluminate to soap ratio is greater than 4 or 5:1, the

excess aluminate that is present is wasted. My preferred ratio is from about 1:1 to about 2 parts aluminate to 1 part soap. It has been found that a ratio of 1.25 parts by weight of aluminate to one part by weight of soap-provides especially advantageous results.

Alkali metal salts of fatty acids having from 10 to 20' carbon atoms are commonly referred to as soaps. Soaps of alkali metals can be made either by saponifying fats andoils, or by neutralizing free fatty acids. In the subject process, it is important that the soaps be soluble in water. For this reason, only sodium, potassium, and cesium soaps are considered to be important. Calcium and magnesium soaps, for example, are highly insoluble in water. The most widely used soaps are sodium stearate,

sodium oleate, sodium laurate, sodium palmitate, and.

mixtures of these salts. Rosin soaps have also been used successfully in my invention as well as coconut oilfatty acid soaps and tall oil fatty acid soaps.

-The alkalimetal aluminate ingredient of the mixture which is described in detail in Lindsay et al., U.S. Paten.t 2,345,134. In the Lindsay et a1. patent, it is suggested that the sodium aluminate solutions be treated with stabilizing agents to prolong their shelf life. Although it is preferred in some instances to use a stabilized sodium aluminate, unstabilized materials can also be employed in the subject process. The molar ratio of Na O to A1 0 canvary considerably, although aluminates having .a, ratio of between about 1:1 and 1.511 are most readily available commercially. Sodium aluminate is my preferred ingredient inasmuch as it is readily available commercially. Potassium aluminate, however, could be used as a substitute for sodium aluminate 'with comparable success.

Atypical commercial sodium aluminate which is well suited for use in preparing my composition is the product' Nalco 680 which has the followingproperties:

Color White.

Odor None. Maximum solubility at 1 parts in parts .water.

Density 50 lbs/cu. ft.

Insoluble Less than 0.2%.

Na OzAl o molecular ratio 1.15:1.

One

A1203, percent 46.0. Na O, percent 31.0. Fe, percent 0.01. Ca and Mg, percent Negative. Si, percent 0.02. Heavy metals, percent Negative. As, percent Negative.

The product may be further characterized by the formula Na20.AI203.3H20- If the soap used in the invention is sodium stearate, the aqueous soap solution can contain from about 0.5 to about 2.5% soap. This range can vary widely. The upper concentration limit is determined by the workability of the solution. If too much soap is present the solution is thick and difiicult to work with. Other soaps such as potassium stearate or sodium oleate are more soluble in water than is sodium stearate. For this reason, solutions containing these soaps can be more concentrated without experiencing any difficulties. The aluminate solution can contain up to as much as 50% or more of aluminate.

One field in which my precipitated product has found unusual success is in the waterproofing of cellulosic fabrics.

A continuous search is being carried out by textile manufacturers and others to find improved methods of waterproofing fabrics. Currently, coatings of wax, rubber, plastic, etc., are used to produce water-repellent finishes on textiles. Particular oils, greases, and silicones have also been applied to fabrics to make them waterproof. Recently, cotton and other materials have been treated with various surface active agents in order to increase their water repellency.

One of the best known of the latter type of waterproofing agents is sold under the trademark Zelan. Zelan has the formula and. is usually prepared by treating stearic amide with formaldehyde, HCl, and pyridine. This material is soluble in water and forms soapy solutions of low surface tension. Solutions of Zelan, buffered with sodium acetate, are applied to fabrics through the use of a pad bath and pad mangles. After the padding, the fabric is dried and subsequently baked at temperatures in the range of 170 to 190 C. for about seventyseconds or longer. again dried.

Although there is some question as to the chemical reactions involved, it is the accepted view that pyridine is given off during the heating step which causes a thin, adherent coating of methylenedistearamide to form on the surface of the fabric. It is this coating which gives the fabric its water-repellent properties. Other waterproofing chemicals of this type include Velan which has the structure [oaHso-oH,-r[ 101- and which is made from octadecyl chloromethyl' ether andPyridine, and Norane which has the structure.

I: 01113350 o om-N 151- and which is made by combining stearic acid chloride,

After the baking step the fabric is rinsed and peratures of 170 to 190 C., for example, often has a harmful effect on the fabric. Additionally, the known waterproofing agents are relatively expensive.

It has been discovered that a superior waterproofing agent can be prepared by combining a water-soluble soap with an alkali metal aluminate (also, an alkali metal salt of zinc, titanium, or tin) and by thereafter contacting the material with an acidic solution. It has been found that cotton and other fabrics which are not sensitive to alkalis can be waterproofed in a simple and inexpensive manner by treating the fabric with a solution containing a soap and either sodium or potassium aluminate and thereafter contacting the fabric with an acidic liquid. The essential steps of the process are as follows:

Fabric Thoroughly wet with alkali metal aluminate-soap solution Dried Thoroughly wet with acid solution l Dried In carrying out the waterproofing method, the fabric is held in the aluminate-soap solution until it is thoroughly wet. It has been found that a treating time of from about 2 to about 30 seconds is sulficient in most instances. After leaving the aluminate-soap solution, the fabric is dried and then dipped in an aqueous acid bath. Once again, the fabric is held in the bath until it is thoroughly wet (usually 2 to about 30 seconds). The fabric could be left in both the aluminate-soap solution or the acid solution for longer periods without damage. This is time consuming, however, and does not improve the waterproofnes-s of the cloth. After the acid bath step, the fabric is again dried.

The selection of the particular acid to be used in the acid bath is not critical. A number of materials such as acetic acid, hydrochloric acid, sulfuric acid, and nitric acid, as well as sebacic and adipic acids have been used successfully in my process. It has also been found that the ammonium salts of these acids provide highly acceptable results. These salts, in fact, are my preferred treating agents, especially where the salts are combined with substantially equal quantities of urea.

The concentration of the acid solutions can vary wide- 1y. Where acetic acid is used, the solution contained from as little as 0.1% acid up to as much as 20% acid. My preferred concentration range is from about 2% to about 4% acetic acid. When using stronger acids such as hydrochloric or sulfuric, the concentration should be somewhat lower. With hydrochloric acid, for example, the concentration should be less than 5%. My preferred amount is from about 0.5% to about 1% HCl.

In most instances the entire waterproofing process can be carried out at room temperatures. It is preferred, in some cases, however, to dry the aluminate-soap solution at temperatures of from about 50 to about C. This is especially true where sodium stearate is the soap ingredient. The aluminate-sodium stearate composition tends to gel at temperatures below about 50 C. Increasing the temperature of the drying step also speeds up the process. High temperatures, however, are not needed to form the waterproofing composition. In no event is it necessary to heat the fabric to temperatures within the range of to C. where scorching might occur.

In the examples which appear below, the following tests were used to determine the waterproofness of a fabric treated with various compounds.

WATERPROOFNESS TEST The waterproofness of the fabric was determined according to the AATCC standard test No. 22-1952. In this test, the specimen is mounted on an embroidery hoop at a 45 angle and water of 80i2 F. is dropped from a sprinkler nozzle on the specimen from a height of 6". Two hundred and fifty (250) ml. of water are used per test. The specimens are graded by referring to a chart of pictures of fabrics wetted in varying degrees. A rating of 100 constituted a perfect score for a sample which was completely waterproof. A score of from about 70 to 100 was considered to be acceptable.

In another test, the specimens were arranged over the opening of a beaker so that they would support a quantity of water one inch deep. The water was allowed to stand on the cloth for two weeks. Where the waterproofing method was satisfactory no leakage occurred during this period.

Example I This example illustrates the preparation of the soap solution (A), the aluminate solution (B), and the final solution (C) as well as the treatment of cotton by the subject waterproofing method.

Solution A (made up of three ingredients):

26 g. of stearic acid 5.6 g. of potassium hydroxide 168.4 g. of water Solution B (made up of two ingredients):

g. of sodium aluminate 85 g. of Water Solution C (made up of three ingredients):

g. of solution A 150 g. of water 30 g. of solution B A small piece of cloth (about 14 x 14" of mercerized cotton cloth) was immersed in solution C, squeezed, and dried on a pin frame at 140 C. for 3 minutes. The cloth was then immersed in a 3% ammonium acetate solution, carefully rinsed, and dried. It was then subjected to the tests described above and found to be very waterproof.

The cotton fabric of Example I was immersed in solution C, squeezed, and dried on a pin frame at about 140* C. for 3 minutes. The cloth was then immersed in a 2% acetic acid solution, carefully rinsed, and dried. It was then subjected to the Waterproofness tests listed above and found to rate about 90 on the standard test. No leakage occurred when water was permitted to stand on the samples.

Example 111 Solution A: G. 12-hydroxystearic acid 30 KOH 5.6 Water 164.4 Solution B:

Unstabilized sodium aluminate 30 Water 170 i The cotton was treated as described in Example II. Its waterproofness rating was about 80%, and no leakage occurred when Water was permitted to stand on the samples.

Example IV Solution A: G. Coconut fatty acids 26 KOH 5.6 Water 174.4

Solution B:

Nalco 680 30 Water 170 Solution C:

Solution A 15 Solution B 20 Water 65 The cloth was treated as in Example II. The waterproofness of the final product was charted to be 100, and no leakage occurred when water was permitted to stand on the samples.

The cotton fabric of Example I was immersed in solu-" tion C, squeezed, and dried on a pin frame at about C. for three minutes. The cloth was then immersed in a 1% solution of hydrochloric acid, carefully rinsed, and dried. It was then subjected to the waterproofness tests listed above and found to rate about 95 on the standard test. No leakage occurred when water was permitted to stand on the samples. More than 90% of the tall oil fraction consisted of approximatley equal parts of oleic and linoleic acids.'

In addition to aluminum, the amphoteric metals zinc, titanium, and tin can also be used in preparing my waterproofing agents.

Example VI Solution A:

26 g. of potassium stearate 5.6 g. of KOH 174.4 g. of water Solution B:

30 g. of potassium titanate 170 g. of water Solution C:

20 g. solution A g. solution B g. of water 7 The cotton fabric of Example I was immersedin solution C, squeezed, and dried on a pin frame at about 110 C. for three minutes. The cloth was then immersed in a 2% solution of acetic acid, carefully rinsed, and dried; It was then subjected to the wate-rpoofing tests described above and was found to rate about 95 on the standard test. No leakage occurred when water was permitted to stand on the samples.

Where zinc or tin is used as the amphoteric metal,

zinc or tin hydroxide is dissolved in NaOH or KOH to form the resulting sodium or potassium zincate-or stannate. When this material is added to a soap such as sodium stearate, a clear solution results at elevated temperatures. A gel forms when the solution is cooled. If cellulosic fabrics are immersed in the solution, dried, then dipped into an acid bath such as a 2% acetic acid bath, and again dried, the resulting fabric is found to have a permanent waterproofness which resists removal by washing or dry cleaning.

The reactions which take place when the sodium aluminate and soap solutions are combined and when the fabrics, impregnated with these materials, are placed in an acid bath are not completely understood. It is thought, however, that the aluminate forms a preliminary bond with the fatty acid when the solution is placed on the fabric and dried. It is further postulated that the aluminum ion forms a bridge between the cellulose molecule and the fatty acid. The addition of the acid or the ammonium salt makes the reaction with the aluminum and the fatty acid complete, so that aluminum compounds are formed right in the cotton where part of the aluminum ion valence is tied directly to the cellulose. This results in an aluminum soap which is difiicult to remove either by washing in water or by dry cleaning. This is in contrast to known fabric waterproofing treatments where soaps are used in making renewable waterproofness treatments which are very easily removed by dry cleaning.

While it is not certain that the above reactions are occurring, it is clear that the waterproofing treatment is more permanent than would be expected if it merely consisted of impregnating cotton fibers with aluminum soap. The stepwise procedures outlined herein are followed to take advantage of this possibility.

The fabrics that can be treated with the subject waterproofing agents are cellulosic materials such as cotton, rayon; and linen. These fabrics are not adversely affected by alkalis.

Although the subject process can be carried out at room temperatures, it is sometimes helpful to use heat in drying the fabrics. In no case, however, is it necessary to bake the fabrics at temperatures which might cause scorching. Another feature of the subject process is that the precipitated soap-aluminate waterproofing material is almost completely unaffected by laundering and dry cleaning processes. No longer is it necessary to rewaterproof a garment after a limited number of washings or dry cleaning operations.

As was indicated above, my compositions are highly effective agents for the sizing of paper. Previously, alum has been used to precipitate sodium rosin to give a bridging through the aluminum ion between the rosin and the paper fiber. By making use of my aluminate-soap solution and by mixing this material intimately with paper fiber before precipitation occurs, one is able to size paper in a more complete manner and at a higher pH than was possible using prior art processes.

The discovery that the viscosity of alkali soap solutions increases appreciably by the addition of sodium aluminate makes it possible to improve the thickness of a shampoo by the use of small amounts of sodium or potassium aluminate. Alkali soaps containing an alkali metal aluminate can also be used to form hand soaps having a relatively high water concentration.

One of the difficulties involved in obtaining a stable oil-in-water emulsion is caused by the low viscosity of water. Oil particles that are suspended in the water continuously collide with each other and coalesce causing the emulsion to break. It has been found that the addition of my soap-aluminate mixture to the water phase of the emulsion causes it to thicken so as to substantially reduce the number of oil particle collisions that take place. This greatly improves the stability of the emulsion. One particularly interesting application of this property is in the formation of asphalt emulsions or cutting oil emulsions. In the latter case it has been found that the soap-aluminate mixture also increases the lubricating properties of the oil.

It has recently been discovered that greases can be thickened by adding fatty amine treated clays to the product. If my sodium aluminate-soap mixture is reacted with "clay, products are produced which have water-repellent properties and which are swellable by lubricating oils to yield useful greases. These greases are much less expensive than the amine products due to the fact that sodium soaps are considerably cheaper than fattty amines.

My sodium aluminate-soap mixtures provide excellent lubricants for metal surfaces. The Water present in the mixture maintains the surfaces of the metal at reasonable temperatures while the thickness of the solution gives the composition excellent lubricating properties.

A considerable amount of interest recently has been expressed in the development of an inexpensive hydraulic fluid which is noninfiammable. Water itself cannot be used as fluid for hydraulic systems because its viscosity is too low and because it has no lubricating properties. It has been found that my soap-aluminate solution increases the viscosity of water and also increases its lubricating properties. For this reason my materials provide a hydraulic fluid which is inexpensive and yet functions satisfactorily.

Example VII This example illustrates the thickening action that a sodium aluminate solution has on a sodium stearate solution. In this test, 28 grams of stearic acid was reacted with 4 g. of sodium hydroxide. A sufficient amount of Water was then added to provide 200 g. of soap solution. Fifteen (15) g. of Nalco 680, which is described above, was dissolved in sufficient water to make g. of the aluminate solution. Ten (10) g. of the sodium stearic solution was then added to 175 g. of water at F. Fifteen (15) g. of the sodium aluminate solution was added to the water. On cooling to room temperature the solution gelled and a soiid was formed. When oleic acid was used in the same test rather than stearic acid, a thick solution was formed rather than a solid.

In addition to the above uses, my products can also serve as coagulants; antifoam agents; flotation agents; ingredients in dyes; ingredients in paint removers and cleaners; stabilizers; etc. The compositions can be used in preparing rayon; in preparing pigments; etc.

The subject invention makes it possible to prepare unusual aluminum, zinc, titanium, and tin soaps in a convenient manner. The soaps can be precipitated by fatty acids or ammonium soaps so as to form mixed prod ucts such as aluminum stearate acetate or aluminum stearate salicylicate, etc. Mixed soaps of this type are readily prepared by my process inasmuch as the fatty acids and aluminate are brought into close proximity before precipitation occurs. When aluminate soaps are precipitated using alum, on the other hand, the pH is reduced at the same time that the aluminum ion is introduced so that there is a strong possibility of also having free fatty acids precipitate due to the lowered pH.

Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

The invention is hereby claimed as follows:

1. A new composition of matter consisting essentially of an aqueous solution containing as a solute (1) an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and (2) a water-soluble soap in a concentration range of from .5 part by Weight of said salt to one part by Weight soap to 10 parts by weight aluminate to one part by Weight soap.

2. A new composition of matter consisting essentially of an aqueous solution containing as a solute (1) an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, Zinc, titanium, and tin, and (2) potassium stearate in a concentration range of from .5 part by weight of said salt to one part by weight potassium stearate to 10 parts by weight of said salt to one part by weight potassium stearate.

3. A new composition of matter consisting of an aqueous solution containing as a solute (1) an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and (2) a water-soluble soap in a concentration range of from one part by weight of said salt to one part by weight of soap to two parts by weight of said salt to one part by weight of said soap.

4. A new composition of matter consisting of an aqueous solution containing as a solute (1) an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and (2) a water-soluble soap in a concentration range of from 1.25 parts by weight of said salt to one part by weight of soap.

5. A cellulosic fabric selected from the group consisting of cotton, rayon, and linen, which fabric is coated with a waterproofing agent formed by applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap and by thereafter contacting said fabric with an acid solution.

6. A cellulosic fabric selected from the group consisting of cotton, rayon, and linen, which fabric is coated with a waterproofing agent formed by applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap selected from the group consisting of the sodium, potassium and ammonium salts of stearic acid, oleic acid, lauric acid, palmitic acid, and rosin acids in a concentration range of from .5 part by weight of said salt to one part by weight soap to parts by weight of said salt to one part by Weight soap; drying said fabric; and by thereafter contacting said fabric with an acid solution.

7. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap; and thereafter contacting said fabric with an acid solution.

8. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap selected from the group consisting of the sodium and potassium salts of fatty acids having from 12 to 20 carbon atoms, and the sodium and potassium salts of rosin acids; and thereafter contacting said fabric with an acid solution.

9. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap selected from the group consisting of the sodium and potassium salts of stearic acid, oleic acid, lauric acid, palmitic acid, and rosin and coconut oil fatty acids; and thereafter contacting said fabric with an acid solution.

10. A process for waterproofing fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap in a concentration range of from .5 .part of said salt to one part soap to 10 parts of said salt to one part soap; drying said fabric and thereafter contacting said fabric with an acid solution.

11. A process for waterproofing fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric a 10 metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a water-soluble soap selected from the group consisting of the sodium and potassium salts of fatty acids having from 12 to 20 carbon atoms, and the sodium and potassium salts of rosin acids; drying said fabric and thereafter contacting said fabric with an acid solution.

12. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a watersoluble soap in a concentration range of from .5 part of said salt to one part soap to 10 parts of said salt to one part soap; and thereafter contacting said fabric with an aqueous acidic solution containing a compound selected from the group consisting of acetic acid, hydrochloric acid, sebacic acid, adipic acid, and the ammonium salts of said acids.

13. A process for waterproofing cellulosic fabrics selected from the group consisting of cotton, linen, and rayon which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a watersoluble soap, said soap being selected from the group consisting of the sodium, potassium and ammonium salts of fatty acids having from 12 to 18 carbon atoms, and the sodium, potassium, and cesium salts of rosin acids, in a ratio of from about .5 part of said salt to one part soap to 10 parts of said salt to one part soap; and thereafter contacting said fabrics with an aqueous solution containing from .1 to 20% by weight of an acid selected from the group consisting of acetic acid, hydrochloric acid, sulfuric acid, nitric acid, and the ammonium salts of said acids.

14. A process for waterproofing cellulosic fabrics selected from the group consisting of cotton, linen, and rayon which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a watersoluble soap, said soap being selected from the group consisting of sodium, potassium, and cesium salts of fatty acids having from 12 to 18 carbon atoms, and the sodium, potassium and cesium salts of rosin acids, in a ratio of from about .5 part of said salt to one part soap to 10 parts of said salt to one part soap; and thereafter contacting said fabric with an aqueous solution containing from about 0.1% to 20% by weight of a compound selected from the group consisting of acetic acid, the ammonium salt of acetic acid, and mixtures thereof.

15. A process for waterproofing cellulosic fabrics selected from the group consisting of cotton, linen, and rayon which comprises: applying to said fabric a solution containing an alkali metal salt of an amphoteric metal, such amphoteric metal being selected from the group consisting of aluminum, zinc, titanium, and tin, and a watersoluble soap, said soap being selected from the group consisting of sodium, potassium and ammonium salts of fatty acids having from 12 to 18 carbon atoms, and the sodium, potassium and ammonium salts of rosin acids, in a ratio of from about .5 part of said salt to one part soap to 10 parts of said salt to one part soap; and thereafter contacting said fabric with an aqueous solution contaming from about 0.1% to 10% by weight of a compound selected from the group consisting of acetic acid, the ammonium salt of acetic acid, and mixtures thereof; and containing approximately an equal amount by weight of urea.

16. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing sodium aluminate and potassium stearate in a ratio of from about .5 part aluminate to one part soap to 10 parts aluminate to one part soap; and thereafter contacting said fabric with an aqueous solution containing from about 2 to about 4% by weight of the ammonium salt of acetic acid and from about 2 to about 4% by weight of urea.

17. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing an alkali metal salt of aluminum and a watersoluble soap; and thereafter contacting said fabric with an acid solution.

18. A process for waterproofing cellulosic fabrics which comprises: applying to said fabric a solution containing sodium aluminate and a water-soluble soap selected from the group consisting of the sodium and potassium salts of fatty acids having from 12 to 20 carbon atoms, and the sodium and potassium salts of rosin acids; and thereafter contacting said fabric with an acid solution.

19. A process for waterproofing cellulosic fabrics selected from the group consisting of cotton, linen, and rayon which comprises: applying to said fabric a solution containing sodium aluminate and a water-soluble soap, said soap being selected from the group consisting of the sodium, potassium and ammonium salts of fatty acids having from 12 to 18 carbon atoms, and the sodium, potassium, and cesium salts of rosin acids, in a ratio of from about .5 part aluminate to one part soap to parts aluminate to one part soap; and thereafter contacting said fabrics with an aqueous solution containing from .1 to 20% by weight of an acid selected from the group consisting of acetic acid, hydrochloric acid, sulfuric acid, nitric acid, and the ammonium salts of said acids.

20. A process for waterproofing cellulosic fabrics selected from the group consisting of cotton, linen, and rayon which comprises: applying to said fabric a solution containing sodium aluminate and a water-soluble soap, said soap being selected from the group consisting of sodium, potassium, and cesium salts of fatty acids having from 12 to 18 carbon atoms, and the sodium, potassium and cesium salts of rosin acids, in a ratio of from about .5 part aluminate to one part soap to 10 parts aluminate to one part soap; and thereafter contacting said fabric with an aqueous solution containing from about 0.1% to 20% by weight of a compound selected from the group consisting of acetic acid, the ammonium salt of acetic acid, and mixtures thereof.

21. A process for waterproofing cellulosic fabrics selected from the group consisting of cotton, linen, and rayon which comprises: applying to said fabric a solution containing sodium aluminate and a water-soluble soap, said soap being selected from the group consisting of sodium, potassium and ammonium salts of fatty acids having from 12 to 18 carbon atoms, and the sodium, potassium and ammonium salts of rosin acids, in a ratio of from about .5 part aluminate to one part soap to 10 parts aluminate to one part soap; and thereafter contacting said fabric with an aqueous solution containing from about 0.1% to 10% by weight of a compound selected from the group consisting of acetic acid, the ammonium salt of acetic acid, and mixtures thereof; and containing approximately an equal amount by weight of urea.

References Cited in the file of this patent UNITED STATES PATENTS 2,095,129 Drew Oct. 5, 1937 2,150,777 Morrill Mar. 14, 1939 2,345,142 Muller Mar. 28, 1944 2,426,300 Edelstein Aug. 26, 1947 2,930,106 Wrotnowski Mar. 29, 1960 OTHER REFERENCES Chemical Abstracts, vol. 51, 6188(h) (1957).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3,081 190 March 12, 1963 Carl E. Johnson hat error appears in the above numbered pat- It is hereby certified t hat the said Letters Patent should read as ent requiring correction and t corrected below.

Column 3, lines 57 to 59, the formula should appear as shown below instead of as in the patent:

column 8, line 66, for "aluminate" read said salt Signed and sealed this day of December 1963.

(SEAL) Attest: EDWIN L, REYNOLDS ERNEST W. SWIDER Attesting Officer Ac ting Commissioner of Patents 

7. A PROCESS FOR WATERPROOFING CELLULOSIC FABRICS WHICH COMPRISES: APPLYING TO SAID FABRIC A SOLUTION CONTAINING AN ALKALI METAL SALT OF AN AMPHOTERIC METAL, SUCH AMPHOTERIC METAL BEING SELECTED FROM THE GROUP CONSISTING OF ALUMINIUM, ZINC, TITANIUM, AND TIN, AND A WATER-SOLUBLE SOAP; AND THEREAFTER CONTACTING SAID FABRIC WITH AN ACID SOLUTION. 